Pesticidal compositions

ABSTRACT

Composition for controlling insects and representatives of the order Acarina, which comprises a combination of variable amounts of one or more compounds of the formula                    
     in which 
     A is an unsubstituted or, depending on the possibility of substitution on the ring system, mono- to tetrasubstituted, aromatic or non-aromatic monocyclic or bicyclic heterocyclic radical, in which the substituents of A are chosen from the group consisting of C 1 -C 3 alkyl, C 1 -C 3 alkoxy, halogen, halo-C 1 -C 3 alkyl, cyclopropyl, halocyclopropyl, C 2 -C 3 alkenyl, C 2 -C 3 alkynyl, halo-C 2 -C 3 alkenyl, halo-C 2 -C 3 alkynyl, halo-C 1 -C 3 alkoxy, C 1 -C 3 alkylthio, halo-C 1 -C 3 alkylthio, allyloxy, propargyloxy, allylthio, propargylthio, haloallyloxy, haloallylthio, cyano and nitro; R is hydrogen, C 1 -C 6 alkyl, phenyl-C 1 -C 4 alkyl, C 3 -C 6 cycloalkyl, C 2 -C 6 alkenyl or C 2 -C 6 alkynyl; and X is N—NO 2  or N—CN, in the free form or in salt form, if appropriate tautomers, in the free form or salt form, and one or more of the compounds: 
     azamethiphos; chlorfenvinphos; cypermethrin, cypermethrin high-cis; cyromazin; diafenthiuron; diazinon; dichlorvos; dicrotophos; dicyclanil; fenoxycarb; fluazuron; furathiocarb; isazofos; jodfenphos; kinoprene; lufenuron; methacriphos; methidathion; monocrotophos; phosphamidon; profenofos; diofenolan; a substance obtainable from a  Bacillus thuringiensis  strain; pymetrozine; bromopropylate; methoprene; disulfuton; quinalphos; tau-fluvalinate; thiocyclam; or thiometon and at least one auxiliary; a method of controlling pests, a process for the preparation of the composition, its use and plant propagation material treated with it, and the use of the compound of the formula (A) for the preparation of the composition are described.

This application is a continuation of Ser. No. 09/171,721 filed Nov. 13,1998 now abandoned, which is based on PCT/EP97/01925 Apr. 17, 1997.

The present invention relates to a composition which comprises apesticidal active compound combination, a method of controlling pestswith this composition, a process for the preparation of the composition,its use and plant propagation material treated with it, and the use of acompound of the following formula (A) for the preparation of thecomposition.

Certain mixtures of active compounds are proposed for pest control inthe literature. However, the biological properties of these mixtures ofknown compounds are not completely satisfactory in the field of pestcontrol, and for this reason there is a need to provide further mixtureshaving synergistic pest control properties, in particular for controlingof insects and representatives of the order Acarina. This object isachieved according to the invention by providing the presentcomposition.

The invention accordingly relates to a composition for controllinginsects or representatives of the order Acarina, which comprises acombination of variable amounts of one or more compounds of the formula

in which

A is an unsubstituted or, depending on the possibility of substitutionon the ring system, mono- to tetrasubstituted, aromatic or non-aromaticmonocyclic or bicyclic heterocyclic radical, in which the substituentsof A are chosen from the group consisting of C₁-C₃alkyl, C₁-C₃alkoxy,halogen, halo-C₁ 14 C₃alkyl, cyclopropyl, halocyclopropyl, C₂-C₃alkenyl,C₂-C₃alkynyl, halo-C₂-C₃alkenyl, halo-C₂-C₃alkynyl, halo-C₁-C₃alkoxy,C₁-C₃-C₃alkylthio, halo-C₁-C₃alkylthio, allyloxy, propargyloxy,allylthio, propargylthio, haloallyloxy, haloallylthio, cyano and nitro;

R is hydrogen, C₁-C₆alkyl, phenyl-C₁-C₄alkyl, C₃-C₆cycloalkyl,C₂-C₆alkenyl or C₂-C₆alkynyl; and

X is N—NO₂ or N—CN,

in the free form or in salt form, if appropriate tautomers, in the freeform or salt form, and one or more of the compounds:

(I) azamethiphos; (XII) furathiocarb; (II) chlorfenvinphos; (XIII)isazofos; (III) cypermethrin, cypermethrin high-cis; (XIV) jodfenphos;(IV) cyromazin; (XV) kinoprene; (V) diafenthiuron; (XVI) lufenuron; (VI)diazinon; (XVII) methacriphos; (VII) dichlorvos; (XVIII) methidathion;(VIII) dicrotophos; (XIX) monocrotophos; (IX) dicyclanil; (XX)phosphamidon; (X) fenoxycarb; (XXI) profenofos; (XI) fluazuron; (XXII)diofenolan; (XXIII) a substance obtainable from the Bacillusthuringiensis strain GC91 or from NCTC11821; (XXIV) pymetrozine;(XXVIII) quinalphos; (XXV) bromopropylate; (XXIX) tau-fluvalinate;(XXVI) methoprene; (XXX) thiocyclam; or (XXVII) disulfuton; (XXXI)thiometon;

and at least one auxiliary.

The compounds of the formula (A) are described in EP-A-580553.

(I) S-6-chloro-2,3-dihydro-2-oxo-1,3-oxazolo[4,5-b]pyridin-3-ylmethylO,O-dimethyl phosphorothioate (azamethiphos) is known from The PesticideManual, 9^(th) Edition (1991), The British Crop Protection Council,London, page 44;

(II) 2-chloro-1-(2,4-dichlorophenyl)vinyl diethyl phosphate(chlorfenvinphos) is known from The Pesticide Manual, 10^(th) Edition(1994), The British Crop Protection Council, London, page 174;

(III) (RS)-α-cyano-3-phenoxybenzyl(1RS)-cis-trans-3-(2,2-dichlorvinyl)-1,1-dimethylcyclo-propanecarboxylate(cypermethrin, cypermethrin high-cis) is known from The PesticideManual, 9^(th) Edition (1991), The British Crop Protection Council,London, page 208;

(IV) N-cyclopropyl-1,3,5-triazine-2,4,6-triamine (cyromazin) is knownfrom The Pesticide Manual, 9^(th) Edition (1991), The British CropProtection Council, London, page 217;

(V) 1-tert-butyl-3-(2,6-diisopropyl-4-phenoxyphenyl)thiourea(diafenthiuron) is known from The Pesticide Manual, 10^(th) Edition(1994), The British Crop Protection Council, London, page 294;

(VI) O,O-diethyl O-2-isopropyl-6-methylpyrimidin-4-yl-phosphorothioate(diazinon) is known from The Pesticide Manual, 9^(th) Edition (1991),The British Crop Protection Council, London, page 243;

(VII) 2,2-dichlorovinyl dimethyl phosphate (dichlorvos), is known fromThe Pesticide Manual, 9^(th) Edition (1991), The British Crop ProtectionCouncil, London, page 259;

(VIII) (E)-2-dimethylcarbamoyl-1-methylvinyl dimethyl phosphate(dicrotophos) is known from The Pesticide Manual, 10^(th) Edition(1994), The British Crop Protection Council, London, page 322;

(IX) 5-cyano-2-cyclopropylamino-4,6-diaminopyrimidine (dicyclanil) isknown from EP-A-244360;

(X) ethyl 2-(4-phenoxyphenoxy)ethylcarbamate (fenoxycarb) is known fromThe Pesticide Manual, 9^(th) Edition (1991), The British Crop ProtectionCouncil, London, page 375;

(XI)1-[4-chloro-3-(3-chloro-5-trifluoromethyl-2-pyridylox)phenyl]-3-(2,6-difluorobenzoyl)-urea(fluazuron) is known from The Pesticide Manual, 10^(th) Edition (1994),The British Crop Protection Council, London, page 475;

(XII) butyl 2,3-dihydro-2,2-dimethylbenzofuran-7-ylN,N′-dimethyl-N,N′-thiodicarbamate (furathiocarb) is known from ThePesticide Manual, 9^(th) Edition (1991), The British Crop ProtectionCouncil, London, page 448;

(XIII) O-5-chloro-1-isopropyl-1H-1,2,4-triazol-3-yl O,O-diethylphosphorothioate (isazofos) is known from The Pesticide Manual, 9^(th)Edition (1991), The British Crop Protection Council, London, page 502;

(XIV) O-2,5-dichloro-4-iodophenyl O,O-dimethylphosphorothioateGodfenphos) is known from The Pesticide Manual, 10^(th) Edition (1994),The British Crop Protection Council, London, page 1102;

(XV) prop-2-ynyl (±) (E,E)-3,7,11-trimethyidodeca-2,4-dienoate(kinoprene) is known from The Pesticide Manual, 10^(th) Edition (1994),The British Crop Protection Council, London, page 1102;

(XVI)(R,S)-1-[2,5-dichloro-4-(1,1,2,3,3,3-hexafluoropropoxy)phenyl]-3-(2,6-difluorobenzoyl)-urea(lufenuron) is known from The Pesticide Manual, 10^(th) Edition (1994),The British Crop Protection Council, London, page 628;

(XVII) methyl (E)-3-(dimethoxyphosphinothioyloxy)-2-methylacrylate(methacriphos) is known from The Pesticide Manual, 9^(th) Edition(1991), The British Crop Protection Council, London, page 562;

(XVIII) S-2,3-dihydro-5-methoxy-2-oxo-1,3,4-thiadiazol-3-ylmethylO,O-dimethyl phosphorodithioate (methidathion) is known from ThePesticide Manual, 9^(th) Edition (1991), The British Crop ProtectionCouncil, London, page 567;

(XIX) dimethyl (E)-1-methyl-2-(methylcarbamoyl)vinyl phosphate(monocrotophos) is known from The Pesticide Manual, 9^(th) Edition(1991), The British Crop Protection Council, London, page 597;

(XX) b 2-chloro-2-diethylcarbamoyl-1-methylvinyl dimethyl phosphate(phosphamidon) is known from The Pesticide Manual, 9^(th) Edition(1991), The British Crop Protection Council, London, page 679;

(XXI) O-4-bromo-2-chlorophenyl O-ethyl S-propyl phosphorothioate(profenofos) is known from The Pesticide Manual, 9^(th) Edition (1991),The British Crop Protection Council, London, page 705;

(XXII) a mixture of 50 to 80% of(2RS,4SR)-4-(2-ethyl-1,3-dioxolan-4-ylmethoxy)phenyl phenyl ether and 50to 20% of (2RS,4RS)-4-(2-ethyl-1,3-dioxolan-4-ylmethoxy)phenyl phenylether (diofenolan) is known from The Pesticide Manual, 10^(th) Edition(1994), The British Crop Protection Council, London, page 363;

(XXIII) a substance obtainable from the Bacillus thuringiensis strainGC91 or a substance obtainable from the Bacillus thuringiensis strainNCTC11821 is known from The Pesticide Manual, 10^(th) Edition (1994),The British Crop Protection Council, London, page 62;

(XXIV)2,3,4,5-tetrahydro-3-oxo-4-[(pyridin-3-yl)-methyleneamino]-6-methyl-1,2,4-triazine(pymetrozine) is known from The Pesticide Manual, 10^(th) Edition(1994), The British Crop Protection Council, London, page 868; and

(XXV) isopropyl 4,4′-dibromobenzilate (bromopropylate) is known from ThePesticide Manual, 9^(th) Edition (1991), The British Crop ProtectionCouncil, London, page 99,

(XXVI) isopropyl(E,E)-(R,S)-11-methoxy-3,7,11-trimethyldodeca-2,4-dienoate (methoprene)is known from The Pesticide Manual, 10^(th) Edition (1994), The BritishCrop Protection Council, London, page 680;

(XXVII) O,O-diethyl S-2-ethylthioethyl phosphorodithioate (disulfuton)is known from The Pesticide Manual, 10^(th) Edition (1994), The BritishCrop Protection Council, London, page 372;

(XXVIII) O,O-diethyl O-quinoxalin-2-yl phosphorothioate (quinalphos) isknown from The Pesticide Manual, 10^(th) Edition (1994), The BritishCrop Protection Council, London, page 890, and

(XXIX) (RS)-α-cyano-3-phenoxybenzylN-(2-chloro-α,α,α-trifluoro-p-tolyl)-D-valinate (tau-fluvalinate) isknown from The Pesticide Manual, 9^(th) Edition (1991), The British CropProtection Council, London, page 428.

(XXX) N,N-dimethyl-1,2,3-trithian-5-yl-amine (thiocyclam) is known fromThe Pesticide Manual, 9^(th) Edition (1991), The Britsh Crop ProtectionCouncil, London, page 816; and

(XXXI) S-2-ethylthioethyl O,O-dimethyl phosphorodithioate (thiometon) isknown from The Pesticide Manual, 9^(th) Edition (1991), The British CropProtection Council, London, page 819.

The compounds of the formula (A) can in some cases be in the form oftautomers. For example, if R is hydrogen, corresponding compounds of theformula (A), i.e. those having a 3-H-4-imino-perhydro-1,3,5-oxadiazinepartial structure, can be in equilibrium with the respective tautomerswhich contain a 4-amino-1,2,5,6-tetrahydro-1,3,5-oxadiazine partialstructure. Compounds of the formula (A) above and below are accordinglyalso to be understood as meaning, where appropriate, correspondingtautomers, even if the latter are not mentioned specifically in eachcase.

Compounds of the formula (A) which contain at least one basic centre canform, for example, acid addition salts. These are formed, for example,with strong inorganic acids such as mineral acids, for exampleperchloric acid, sulfuric acid, nitric acid, nitrous acid, a phosphoricacid or a hydrogen halide acid, with strong organic carboxylic acids,such as C₁-C₄alkanecarboxylic acids which are unsubstituted orsubstituted, for example by halogen, for example acetic acid, such asdicarboxylic acids which are saturated or unsaturated, for exampleoxalic, malonic, succinic, maleic, fumaric or phthalic acid, such ashydroxycarboxylic acids, for example ascorbic, lactic, malic, tartaricor citric acid, or such as benzoic acid, or with organic sulfonic acids,such as C₁-C₄alkane- or arylsulfonic acids which are unsubstituted orsubstituted, for example by halogen, for example methane- orp-toluenesulfonic acid. Compounds of the formula (A) with at least oneacid group can furthermore form salts with bases. Suitable salts withbases are, for example, metal salts, such as alkali metal or alkalineearth metal salts, for example sodium, potassium or magnesium salts, orsalts with ammonia or an organic amine, such as morpholine, piperidine,pyrrolidine, a mono-, di- or tri-lower alkylamine, for example ethyl-,diethyl-, triethyl- or dimethyl-propyl-amine, or a mono-, di- ortrihydroxy-lower alkylamine, for example mono-, di- or triethanolamine.If appropriate, corresponding inner salts can furthermore be formed.Agrochemically advantageous salts are preferred in the context of theinvention. As a result of the close relationship between the compoundsof the formula (A) in the free form and in the form of their salts, thefree compounds of the formula (A) and their salts above and below arealso appropriately and expediently to be understood as meaning, whereappropriate, the corresponding salts and the free compounds of theformula (A). The same applies correspondingly to tautomers of compoundsof the formula (A) and salts thereof. In each case the free form is ingeneral preferred.

Compositions which comprise the compound of the formula (A) in the freeform are preferred in the context of the present invention.

The general terms used above and below have the meanings given below,unless defined otherwise.

Heteroatoms in the cyclic base structure of the heterocyclic radical Rare all elements of the Periodic Table which can form at least twocovalent bonds. N and S are preferred.

Halogen—as a group per se and as a structural element of other groupsand compounds, such as of haloalkyl, haloalkylthio, haloalkoxy,halocyclopropyl, haloalkenyl, haloalkynyl, haloallyloxy andhaloallylthio—is fluorine, chlorine, bromine or iodine, in particularfluorine, chlorine or bromine, especially fluorine or chlorine, inparticular chlorine.

Unless defined otherwise, carbon-containing groups and compounds in eachcase contain 1 up to and including 6, preferably 1 up to and including3, in particular 1 or 2, carbon atoms.

Cycloalkyl is cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl,preferably cyclopropyl.

Alkyl—as a group per se and as a structural element of other groups andcompounds, such as of phenylalkyl, haloalkyl, alkoxy, haloalkoxy,alkylthio and haloalkylthio—is, in each case taking into dueconsideration the number of carbon atoms contained from case to case inthe corresponding group or compound, either straight-chain, i.e. methyl,ethyl, propyl, butyl, pentyl or hexyl, or branched, for exampleisopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl orisohexyl.

Alkenyl, haloalkenyl, alkynyl and haloalkynyl are straight-chain orbranched and in each case contain two or preferably one unsaturatedcarbon-carbon bond(s). The double or triple bonds of these substituentsare preferably separated from the remaining part of the compound of theformula (A) by at least one saturated carbon atom. Examples are allyl,methallyl, but-2-enyl, but-3-enyl, propargyl, but-2-ynyl and but-3-ynyl.

Halogen-substituted carbon-containing groups and compounds, such ashaloalkyl, haloalkylthio, haloalkoxy, halocyclopropyl, haloalkenyl,haloalkynyl, haloallyloxy and haloallylthio, can be partly halogenatedor perhalogenated, and in the case of multiple halogenation, the halogensubstituents can be identical or different. Examples of haloalkyl—as agroup per se and as a structural element of other groups and compounds,such as of haloalkylthio and haloalkoxy—are methyl which is mono- totrisubstituted by fluorine, chlorine and/or bromine, such as CHF₂ orCF₃; ethyl which is mono- to pentasubstituted by fluorine, chlorineand/or bromine, such as CH₂CF₃, CF₂CF₃, CF₂CCl₃, CF₂CHCl₂, CF₂CHF₂,CF₂CFCl₂, CF₂CHBr₂, CF₂CHClF, CF₂CHBrF or CClFCHClF; propyl or isopropylwhich is mono- to heptasubstituted by fluorine, chlorine and/or bromine,such as CH₂CHBrCH₂Br, CF₂CHFCF₃, CH₂CF₂CF₃, CF₂CF₂CF₃ or CH(CF₃)₂; andbutyl or one of its isomers which is mono- to nonasubstituted byfluorine, chlorine and/or bromine, such as CF(CF₃)CHFCF₃, CF₂(CF₂)₂CF₃or CH₂(CF₂)₂CF₃. Examples of haloalkenyl are 2,2-difluoroethen-1-yl,2,2- dichloroethen-1-yl, 2-chloroprop-1-en-3-yl,2,3-dichloroprop-1-en-3-yl and 2,3-dibromoprop-1-en-3-yl. Examples ofhaloalkynyl are 2-chloroprop-1-yn-3-yl, 2,3-dichloroprop-1-yn-3-yl and2,3-dibromoprop-1-yn-3-yl. Examples of halocyclopropyl are2-chlorocyclopropyl, 2,2-difluorocyclopropyl and2-chloro-2-fluoro-cyclopropyl. Examples of haloallyloxy are 2-chloroprop1-en-3-yloxy, 2,3-dichloroprop-1-en-3-yloxy and2,3-dibromoprop-1-en-3-yloxy. Examples of haloallylthio are2-chloroprop-1-en-3-ylthio, 2,3-dichloroprop-1-en-3-ylthio and2,3-dibromoprop-1-en-3-ylthio.

In phenylalkyl, an alkyl group bonded to the remaining part of thecompound of the formula (A) is substituted by a phenyl group, the alkylgroup preferably being straight-chain and the phenyl group preferablybeing bonded to the alkyl group in a position higher than theα-position, in particular in the Ω-position; examples are benzyl,2-phenylethyl and 4-phenylbutyl.

Particularly preferred compounds of the formula (A) are those in which

(1) R is hydrogen, C₁-C₄alkyl, C₃-C₆cycloalkyl, C₂-C₆alkenyl orC₂-C₆alkynyl, in particular H or CH₃;

(2) the cyclic base skeleton of A contains 2 to 4, preferablyconjugated, double bonds, preferably contains 2, preferably conjugated,double bonds, and in particular has aromatic character,

(3) the cyclic base skeleton of A contains 1 up to and including 4, inparticular 1 up to and including 3, especially 1 or 2, heteroatoms,particularly preferably 2 heteroatoms;

(4) the cyclic base skeleton of A contains 1, 2 or 3 heteroatoms chosenfrom the group consisting of oxygen, sulfur and nitrogen, not more thanone of the heteroatoms contained in the cyclic base skeleton being anoxygen or sulfur atom, preferably at least one nitrogen atom;

(5) a compound of the formula (A) in which A is mono or disubstituted bysubstituents chosen from the group consisting of halogen and C₁-C₃alkyl,in particular by halogen, especially by chlorine;

(6) a compound of the formula (A) in which the cyclic base skeleton of Ais a pyridyl, 1-oxidopyridinio or thiazolyl group, preferably the cyclicbase skeleton of A is a pyrid-3-yl-, 1-oxido-3-pyridinio or thiazol-5-ylgroup, in particular A is a pyrid-3-yl, 2-halopyrid-5-yl,2,3-dihalopyrid-5-yl, 2-C₁-C₃alkylpyrid-5-yl, 1-oxido-3-pyridinio,2-halo-1-oxido-5-pyridinio, 2,3-dihalo-1-oxido-5-pyridinio or2-halothiazol-5-yl group, A is especially a pyrid-3yl, 2-halopyrid-5-yl,2-halo-1-oxido-5-pyridinio or 2-halothiazol-5-yl group, preferably A isa 2-chloropyrid-5-yl, 2-methylpyrid-5-yl, 1-oxido-3-pyridinio,2-chloro-1-oxido-5-pyridinio, 2,3-dichloro-1-oxido-5-pyridinio or2-chlorothiazol-5-yl group, A is especially a pyrid-3-yl,2-chloropyrid-5-yl, 2-chloro-1-oxido-5-pyridinio or 2-chlorothiazol-5-ylgroup, in particular A is a 2-chloropyrid-5-yl or, preferably,2-chlorothiazol-5-yl group;

(7) a compound of the formula (A), in which X is N—NO₂;

(8) a compound of the formula (A), in which A is a 2-chlorothiazol-5-ylor 2-chloropyrid-5-yl group, R is C₁-C₄alkyl and X is N—NO₂.

Compounds of the formula (A) which are named as preferred in the contextof the invention are

(A.1)5-(2-chloropyrid-5-ylmethyl)-3-methyl-4-nitroimino-perhydro-1,3,5-oxadiazine;

(A.2)5-(2-chlorothiazol-5-ylmethyl)-3-ethyl-4-nitroimino-perhydro-1,3,5-oxadiazine;

(A.3)3-methyl-4-nitroimino-5-(1-oxido-3-pyridiniomethyl)-perhydro-1,3,5-oxadiazine;

(A.4)5-(2-chloro-1-oxido-5-pydidiniomethyl)-3-methyl-4-nitroimino-perhydro-1,3,5-oxadiazine;

(A.5)5-(2-chlorothiazol-5-ylmethyl)-3-methyl-4-nitroimino-perhydro-1,3,5-oxadiazine;

(A.6)3-methyl-5-(2-methylpyrid-5-ylmethyl)-4-nitroimino-perhydro-1,3,5-oxadiazine;

(A.7)3-(2-chloropyrid-5-ylmethyl)-4-nitroimino-perhydro-1,3,5-oxadiazine; and

(A.8)3-(2-chlorothiazol-5-ylmethyl)-4-nitroimino-perhydro-1,3,5oxadiazine.

A composition which, in addition to the compound of the formula (A),comprises only one other pesticidally active compound (I) to (XXXI) isalso preferred. A composition which comprises the compound5-(2-chlorothiazol-5-ylmethyl)-3-methyl-4-nitroimino-perhydro-1,3,5-oxadiazineas active component (A) is likewise preferred. Compositions which, inaddition to a compound of the formula (A), comprise azamethiphos,cypermethrin high-cis, fenoxycarb, diofenolan, profenofos or pymetrozineare furthermore preferred.

The active compound combination according to the invention preferablycomprises the active compound of the formula (A) and one of the activecompounds (I) to (XXXI) in a mixing ratio of 100:1 to 1:6000, inparticular 1:50 to 50:1, in particular in a ratio of between 1:20 and20:1, in particular between 10:1 and 1:10, especially between 5:1 and1:5, particularly preferably between 2:1 and 1:2, and also preferablybetween 4:1 and 2:1, especially in the ratio of 1:1, or 5:1, or 5:2, or5:3, or 5:4, or 4:1, or 4:2, or 4:3, or 3:2, or 2:1, or 1:5, or 2:5, or3:5, or 4:5, or 1:4, or 2:4, or 3:4, or 1:3, or 2:3, or 1:2, or 1:600,or 1:300, or 1:150, or 1:35, or 2:35, or 4:35, or 1:75, or 2:75, or4:75, or 1:6000, or 1;3000, or 1:1500, or 1:350, or 2:350, or 4:350, or1:750, or 2:750, or 4:750. These ratios are understood as meaning weightratios on the one hand, but also molar ratios on the other hand.

It has now been found, surprisingly, that the combination of the activecompound of the formula (A) or of one of its salts with one of theactive compounds (I) to (XXXI) not only causes an additive increase inthe action spectrum on the pests to be controlled, which is to beexpected in principle, but also achieves a synergistic effect whichextends the action limits of both preparations under two aspects:

On the one hand, the rates of application of the compound of the formula(A) and of the individual compounds (I) to (XXXI) are lowered for thesame good action. On the other hand, the combined mixture also still hasa high degree of pest control where the two individual substances havebecome completely inactive in the range of low rates of application.This allows on the one hand a considerable extension to the spectrum ofpests which can be controlled, and on the other hand an increase inapplication reliability.

In addition to the actual synergistic action in respect of pesticidalactivity, however, the compositions according to the invention alsoadditionally have further surprising advantages which can likewise bedescribed as synergistic in a broadened sense: thus, for example, it ispossible to control pests which cannot be controlled or sufficientlyeffectively controlled with the individual compounds(A) or (I) to(XXXI), and the compositions according to the invention have a bettertoleration by plants, i.e. a reduced phytotoxicity, than the individualcompounds (A) and (I) to (XXXI). The insects can furthermore becontrolled in their various stages of development, which is not alwaysthe case with the individual compounds (A) and (I) to (XXXI), sincethese compounds can be used, for example, only as adulticides or only aslarvicides against quite specific larval stages. In addition,combinations of the compound (A) with certain compounds (I) to (XXXI)show more favourable properties during grinding, mixing, storage andalso spraying.

The compositions according to the invention are already valuablepreventively and/or curatively at low rates of concentration in thefield of pest control, while being tolerated by warm-blooded animals,fishes and plants, and have a very favourable biocidal spectrum. Thecompositions according to the invention are active against all orindividual stages of development of normally sensitive and alsoresistant animal pests, such as insects and representatives of the orderAcarina. The insecticidal and/or acaricidal action of the compositionsaccording to the invention can manifest itself here directly, i.e. in adestruction of the pests, which occurs immediately or only after sometime, for example during moulting, or indirectly, for example in areduced oviposition and/or hatching rate, the good action correspondingto a rate of destruction (mortality) of at least 50 to 60%.

The animal pests include, for example:

from the order Lepidoptera

Acleris spp., Adoxophyes spp., Aegeria spp., Agrotis spp., Alabamaargillaceae, Amylois spp., Anticarsia gemmatalis, Archips spp.,Argyrotaenia spp., Autographa spp., Busseola fusca, Cadra cautella,Carposina nipponensis, Chilo spp., Choristoneura spp., Clysiaambiguella, Cnaphalocrocis spp., Cnephasia spp., Cochylis spp.,Coleophora spp., Crocidolomia binotalis, Cryptophlebia leucotreta, Cydiaspp., Diatraea spp., Diparopsis castanea, Earias spp., Ephestia spp.,Eucosma spp., Eupoecilia ambiguella, Euproctis spp., Euxoa spp.,Grapholita spp., Hedya nubiferana, Heliothis spp., Hellula spp.,Hyphantria cunea, Keiferia lycopersicella, Leucoptera scitella,Uthocollethis spp., Lobesia botrana, Lymantria spp., Lyonetia spp.,Malacosoma spp., Mamestra brassicae, Manduca sexta, Operophtera spp.,Ostrinia nubilalis, Pammene spp., Pandemis spp., Panolis flammea,Pectinophora gossypiella, Phthorimaea operculella, Pieris rapae, Pierisspp., Plutella xylostella, Prays spp., Scirpophaga spp., Sesamia spp.,Sparganothis spp., Spodoptera spp., Synanthedon spp., Thaumetopoea spp.,Tortrix spp., Trichoplusia ni and Yponomeuta spp.;

from the order Coleoptera, for example

Agriotes spp., Anthonomus spp., Atomaria linearis, Chaetocnema tibialis,Cosmopolites spp., Curculio spp., Dermestes spp., Diabrotica spp.,Epilachna spp., Eremnus spp., Leptinotarsa decemlineata, Lissorhoptrusspp., Melolontha spp., Oryzaephilus spp., Otiorhynchus spp., Phlyctinusspp., Popillia spp., Psylliodes spp., Rhizopertha spp., Scarabeidae,Sitophilus spp., Sitotroga spp., Tenebrio spp., Tribolium spp. andTrogoderma spp.;

from the order Orthoptera, for example

Blatta spp., Blattella spp., Gryllotalpa spp., Leucophaea maderae,Locusta spp., Periplaneta spp. and Schistocerca spp.;

from the order Isoptera, for example

Reticulitermes spp.;

from the order Psocoptera, for example

Uposcelis spp.;

from the order Anoplura, for example

Haematopinus spp., Linognathus spp., Pediculus spp., Pemphigus spp. andPhylloxera spp;

from the order Mallophaga, for example

Damalinea spp. and Trichodectes spp.;

from the order Thysanoptera, for example

Frankliniella spp., Hercinothrips spp., Taeniothrips spp., Thrips palmi,Thrips tabaci and Scirtothrips aurantli;

from the order Heteroptera, for example

Cimex spp., Distantiella theobroma, Dysdercus spp., Euchistus spp.Eurygaster spp. Leptocorisa spp., Nezara spp., Piesma spp., Rhodniusspp., Sahibergetla singularis, Scotinophara spp. and Triatoma spp.;

from the order Homoptera, for example

Aleurothrixus floccosus, Aleyrodes brassicae, Aonidiella spp.,Aphididae, Aphis spp., Aspidliotus spp., Bemisia tabaci, Ceroplasterspp., Chrysomphalus aonidium, Chrysomphalus dictyospermi, Coccushesperidum, Empoasca spp., Eriosoma lanigerum, Erythroneura spp.,Gascardia spp., Laodelphax spp., Lecanium comi, Lepidosaphes spp.,Macrosiphus spp., Myzus spp., Nephotettix spp., Nilaparvata spp.,Paratoria spp., Pemphigus spp., Planococcus spp., Pseudaulacaspis spp.,Pseudococcus spp., Psylia spp., Pulvinaria aethiopica, Quadraspidiotusspp., Rhopalosiphum spp., Saissetia spp., Scaphoideus spp., Schizaphisspp., Sitobion spp., Trialeurodes vaporariorum, Trioza erytreae andUnaspis citri;

from the order Hymenoptera, for example

Acromyrmex, Atta spp., Cephus spp., Diprion spp., Diprionidae, Gilpiniapolytoma, Hoplocampa spp., Lasius spp., Monomorium pharaonis, Neodiprionspp., Solenopsis spp. and Vespa spp.;

from the order Diptera, for example

Aedes spp., Antherigona soccata, Biblo hortulanus, Calliphoraerythrocephala, Ceratifis spp., Chrysomyia spp., Culex spp., Outerebraspp., Dacus spp., Drosophila melanogaster, Fannia spp., Gastrophilusspp., Glossina spp., Hypodermna spp., Hyppobosca spp., Uriomyza spp.,Lucitia spp., Melanagromyza spp., Musca spp., Oestrus spp., Orseoliaspp., Oscinella frit, Pegomyia hyoscyami, Phorbia spp., Rhagoletispomonella, Sciara spp., Stomoxys spp., Tabanus spp., Tannia spp. andTipula spp.;

from the order Siphonaptera, for example

Ceratophyllus spp. and Xenopsylla cheopis;

from the order Thysanura, for example

Lepisma saccharina and

from the order Acarina, for example

Acarus siro, Aceria sheldoni, Aculus schlechtendali, Amblyomma spp.,Argas spp., Boophilus spp., Brevipalpus spp., Bryobia praetiosa,Calipitrimerus spp., Chorioptes spp., Dermanyssus gallinae,Eotetranychus carpini, Eriophyes spp., Hyalomma spp., Ixodes spp.,Olygonychus pratensis, Omithodoros spp., Panonychus spp., Phyllocoptrutaoleivora, Polyphagotarsonemus latus, Psoroptes spp., Rhipicephalus spp.,Rhizoglyphus spp., Sarcoptes spp., Tarsonemus spp. and Tetranychus spp.

Using the active compound mixtures according to the invention, inparticular pests of the type mentioned which occur on plants, especiallyuseful plants and omamentals in agriculture, in horticulture and inforestry, or on parts such as fruit, blossom, foliage, stems, tubers, orroots, of such plants can be controlled, i.e. checked or destroyed; insome cases even parts of plants which grow later are still protectedfrom these pests.

The pesticidal mixture according to the invention can advantageously beemployed for pest control in cereals, such as maize or sorghum; infruit, for example pome, stone and soft fruit, such as apples, pears,plums, peaches, almonds, cherries or berries, for example strawberries,raspberries and blackberries; in leguminous plants, such as beans,lentils, peas or soya; in oil-bearing crops, such as oilseed rape,mustard, poppy, olive, sunflower, coconut, castor, cacao or groundnuts;in cucurbits, such as pumpkins, cucumbers or melons; in fibre plants,such as cotton, flax, hemp or jute; in citrus fruits, such as oranges,lemons, grapefruits or mandarins; in vegetables, such as spinach,lettuce, asparagus, cabbage varieties, carrots, onions, tomatoes,potatoes or capsicum; in laurareous plants, such as avocado, cinnamoniumor camphor; or in tobacco, nuts, coffee, aubergines, sugar cane, tea,pepper, vines, hops, musaceous plant, natural rubber plants orornamentals, in particular in maize, sorghum, pome and stone fruits,leguminous plants, gourds, cotton, citrus fruits, vegetables,aubergines, vines, hops or ornamentals, especially in maize, sorghum,apples, pears, plums, peaches, beans, peas, soya, olives, sunflowers,coconut, cacao, groundnuts, cucumbers, pumpkins, citrus fruits, cabbagevarieties, tomatoes, potatoes, vines or cotton, particularly preferablyin vines, citrus fruits, apples, pears, tomatoes and cotton.

Other fields of use of the active compound mixtures according to theinvention are protection of stored products and stocks and of material,and in the hygiene sector, in particular the protection of domesticanimals and productive livestock against pests of the type mentioned.

Depending on the aims to be achieved and the given circumstances, thepesticides according to the invention are emulsifiable concentrates,suspension concentrates, directly sprayable or dilutable solutions,spreadable pastes, dilute emulsions, sprayable powders, soluble powders,dispersible powders, wettable powders, dusts, granules or encapsulationsin polymeric substances which comprise the compound of the formula (A)or one of its salts and one of the other active compounds (I) to (XXXI)according to the invention.

The active compounds are employed in these compositions in a pure form,the solid active compounds, for example, being employed in a specificparticle size, or, preferably, together with—at least—one of theauxiliaries conventionally used in the art of formulation, such asextenders, for example solvents or solid carriers, or such assurface-active compounds (surfactants).

Solvents are, for example: non-hydrogenated or partly hydrogenatedaromatic hydrocarbons, preferably fractions C₈ to C₁₂ of alkylbenzenes,such as xylene mixtures, alkylated naphthalenes ortetrahydronaphthalene, aliphatic or cycloaliphatic hydrocarbons, such asparaffins or cyclohexane, alcohols, such as ethanol, propanol orbutanol, glycols and ethers and esters thereof, such as propyleneglycol, dipropylene glycol ether, ethylene glycol or ethylene glycolmonomethyl or -ethyl ether, ketones, such as cyclohexanone, isophoroneor diacetone alcohol, strongly polar solvents, such asN-methylpyrrolid-2-one, dimethyl sulfoxide or N,N-dimethylformamide,water, non-epoxidized or epoxidized plant oils, such as non-epoxidizedor epoxidized rapeseed, castor, coconut or soya oil, and silicone oils.

Solid carriers, for example for dusts and dispersible powders, which areas a rule used are natural rock powders, such as calcite, talc, kaolin,montmorillonite or attapulgite. Highly disperse silicic acids or highlydisperse absorbent polymers can also be added to improve the physicalproperties. Granular, adsorptive granule carriers are porous types, suchas pumice, crushed brick, sepiolite or bentonite, and non-adsorptivecarrier materials are calcite or sand. A large number of granulatedmaterials of inorganic or organic nature, in particular dolomite orcomminuted plant residues, can furthermore be used.

Surface-active compounds are, depending on the nature of the activecompound to be formulated, nonionic, cationic and/or anionic surfactantsor surfactant mixtures having good emulsifying, dissolving and wettingproperties. The surfactants listed below are to be regarded only asexamples here; many other surfactants which are conventionally used inthe art of formulation and are suitable according to the invention aredescribed in the relevant literature.

Nonionic surfactants are, in particular, polyglycol ether derivatives ofaliphatic or cycloaliphatic alcohols, saturated or unsaturated fattyacids and alkylphenols, which can contain 3 to 30 glycol ether groupsand 8 to 20 carbon atoms in the (aliphatic) hydrocarbon radical and 6 to18 carbon atoms in the alkyl radical of the alkylphenols. Water-solubleadducts, containing 20 to 250 ethylene glycol ether groups and 10 to 100propylene glycol ether groups, of polyethylene oxide on polypropyleneglycol, ethylenediaminopolypropylene glycol and alkyl polypropyleneglycol having 1 to 10 carbon atoms in the alkyl chain are furthermoresuitable. The compounds mentioned usually comprise 1 to 5 ethyleneglycol units per propylene glycol unit. Examples arenonylphenol-polyethoxyethanols, castor oil polyglycol ether,polypropylenelpolyethylene oxide adducts,trbutylphenoxypolyethoxyethanol, polyethylene glycol andoctylphenoxypolyethoxyethanol. Fatty acid esters ofpolyoxyethylene-sorbitan, such as polyoxyethylene-sorbitan trioleate,are furthermore possible.

Cationic surfactants are, in particular, quaternary ammonium salts whichcontain, as substituents, at least one alkyl radical having 8 to 22 Catoms and, as further substituents, lower, non-halogenated orhalogenated alkyl, benzyl or lower hydroxy alkyl radicals. The salts arepreferably in the form of halides, methyl sulfates or ethyl sulfates.Examples are stearyltrimethylammonium chloride andbenzyldi(2-chloroethyl)ethylammonium bromide.

Suitable inorganic surfactants can be both water-soluble soaps andwater-soluble synthetic surface-active compounds. Suitable soaps are thealkali metal, alkaline earth metal and substituted and unsubstitutedammonium salts of higher fatty acids (C₁₀-C₂₂), such as the sodium orpotassium salts of oleic or stearic acid, or of naturally occurringfatty acid mixtures, which can be obtained, for example, from coconutoil or tall oil; and furthermore also the fatty acid methyltaurinesalts. However, synthetic surfactants are more frequently used, inparticular fatty sulfonates, fatty sulfates, sulfonated benzimidazolederivatives or alkylarylsulfonates. The fatty sulfonates and sulfatesare as a rule in the form of alkali metal, alkaline earth metal orsubstituted or unsubstituted ammonium salts, and in general contain analkyl radical having 8 to 22 C atoms, alkyl also including the alkylmoiety of acyl radicals; examples are the sodium or calcium salt ofligninsulfonic acid, of dodecylsulfuric acid ester or of a fatty alcoholsulfate mixture prepared from naturally occurring fatty acids. Thesealso include the salts of sulfuric acid esters and sulfonic acids offatty alcohol-ethylene oxide adducts. The sulfonated benzimidazolederivatives preferably contain two sulfonic acid groups and one fattyacid radical having about 8 to 22 C atoms. Alkylarylsulfonates are, forexample, the sodium, calcium or triethanolammonium salts ofdodecylbenzenesulfonic acid, of dibutyinaphthalenesulfonic acid or of anaphthalenesulfonic acid-formaldehyde condensation product.Corresponding phosphates, such as salts of the phosphoric acid ester ofa p-nonylphenol-(4-14)-ethylene oxide adduct or phospholipids, arefurthermore also suitable.

The compositions as a rule comprise 0.1 to 99%, in particular 0.1 to95%, of a mixture of the active compound of the formula (A) with one ofthe active compounds (I) to (XXXI), and 1 to 99.9%, in particular 5 to99.9%, of—at least—one solid or liquid auxiliary, where as a rule 0 to25%, in particular 0.1 to 20%, of the compositions can be surfactants (%is in each case percent by weight). While concentrated compositions arerather preferred as commercial goods, the end user as a rule uses dilutecompositions which have considerably lower active compoundconcentrations. Preferred compositions have, in particular, thefollowing composition (%=percent by weight):

Emulsifiable concentrates: Active compound mixture 1 to 90%, preferably5 to 20% Surfactant: 1 to 30%, preferably 10 to 20% Solvent: 5 to 98%,preferably 70 to 85% Dusts: Active compound mixture: 0.1 to 10%,preferably 0.1 to 1% Solid carrier 99.9 to 90%, preferably 99.9 to 99%Suspension concentrates: Active compound mixture: 5 to 75%, preferably10 to 50% Water: 94 to 24%, preferably 88 to 30% Surfactant: 1 to 40%,preferably 2 to 30% Wettable powders: Active compound mixture: 0.5 to90%, preferably 1 to 80% Surfactant: 0.5 to 20%, preferably 1 to 15%Solid carrier: 5 to 99%, preferably 15 to 98% Granules Active compoundmixture: 0.5 to 30%, preferably 3 to 15% Solid carrier: 99.5 to 70%,preferably 97 to 85%

The compositions according to the invention can also comprise othersolid or liquid auxiliaries such as stabilizers, for examplenon-epoxidized or epoxidized plant oils (for example epoxidized coconutoil, rapeseed oil or soya oil), defoamers, for example silicone oil,preservatives, viscosity regulators, binders and/or tackifiers, as wellas fertilizers or other active compounds for achieving specific effects,for example bactericides, fungicides, nematicides, molluscicides orherbicides.

The compositions according to the invention are prepared in a knownmanner, in the absence of auxiliaries, for example, by grinding, sievingand/or pressing a solid active compound or active compound mixture, forexample to a particular particle size, and in the presence of at leastone auxiliary, for example, by intimate mixing and/or grinding of theactive compound or active compound mixture with the auxiliary orauxilaries. The invention therefore also relates to a process for thepreparation of the compositions.

Mixtures of a compound of the formula (A) with one or more of thecompounds (I) to (XXXI) are preferably employed with the auxiliariesconventionally used in the art of formulation, and are thereforeprocessed, for example, to emulsifiable concentrates, directly sprayableor dilutable solutions, dilute emulsions, wettable powders, solublepowders, dusts and granules, and also to encapsulations in, for example,polymeric substances, in a known manner. The methods of application,such as spraying, atomizing, dusting, wetting, scattering or pouring arechosen, as is the nature of the composition, according to the aims to beachieved and the given circumstances.

The invention furthermore relates to the methods of application of thecompositions, i.e. the methods of controlling pests of the typementioned, such as spraying, atomizing, dusting, spreading, dressing,scattering or pouring, to be chosen according to the aims to be achievedand the given circumstances, and the use of the compositions forcontrolling pests of the type mentioned. Typical rates of concentrationhere are between 0.1 and 1000 ppm, preferably between 0.1 and 500 ppm,of active compound. The rate of application can vary within wide limitsand depends on the nature of the soil, the nature of the application,(leaf application; seed dressing; application in the seed furrow), thecrop plant, the pest to be controlled, the particular climaticcircumstances which prevail and other factors determined by the natureof the application, the time of application and the target crop. Therates of application per hectare are in general 1 to 2000 g of activecompound per hectare, in particular 10 to 1000 g/ha, preferably 20 to600 g/ha.

A preferred method of application in the field of crop protection isapplication to the foliage of the plants (foliar application), where thefrequency of application and rate of application can be chosen accordingto the risk of infestation by the particular pest. However, the activecompound can also enter the plants via the root system (systemic action)by impregnating the locus of the plants with a liquid composition orintroducing the active compounds in solid form into the locus of theplants, for example into the soil, for example in the form of granules(soil application). In paddy rice crops, such granules can be meteredonto the flooded rice field.

The compositions according to the invention are also suitable for theprotection of plant propagation material, for example seeds, such asfruit, tubers, or grain, or plant seedlings, against animal pests. Thepropagation material can be treated with the composition before beingbrought out, for example seed can be dressed before sowing. The activecompounds according to the invention can also be applied to the seedgrains (coating) either by impregnating the grains in a liquidcomposition or coating them with a solid composition. The compositioncan also be applied to the site where the propagation material isbrought out, during broadcasting, for example into the seed furrowduring sowing. The invention furthermore relates to these treatmentmethods for plant propagation material and the plant propagationmaterial treated in this way.

The following examples serve to illustrate the invention. They do notlimit the invention.

Formulation examples (%=percent by weight, active compound ratios=weightratios)

Example F1: Emulsion concentrates a) b) c) Active compound mixture[Compound (A): 25% 40% 50% Compound (I) to (XXXI) = 1:3] Calciumdodecylbenzenesulfonate 5% 8% 6% Castor oil polyethylene glycol ether(36 mol of EO) 5% Tributylphenol polyethylene glycol ether 12% 4% (30mol of EO) Cyclohexanone 15% 20% Xylene mixture 65% 25% 20%

EO is the degree of ethoxylation of castor oil or tributylphenol.

Emulsions of any desired concentration can be prepared from suchconcentrates by dilution with water.

Example F2: Solutions a) b) c) d) Active compound mixture [Compound (A):80% 10% 5% 95% Compound (I) to (XXXI) = 1:10] Ethylene glycol monomethylether 20% Polyethylene glycol molecular wt. 400 — 70%N-methyl-2-pyrrolidone 20% — Epoxidized coconut oil 1% 5% Benzine(boiling limit 160-190° C.) 94%

The solutions are suitable for use in the form of tiny drops.

Example F3: Granules a) b) c) d) Active compound mixture [Compound (A):5% 10% 8% 21% Compound (I) to (XXXI) = 2:1] Kaolin 94% 79% 54% Highlydisperse silicic acid 1% 13% 7% Attapulgite 90% 18%

The active compounds are dissolved together in methylene chloride, thesolution is sprayed onto the carrier and the solvent is then evaporatedoff in vacuo.

Example F4: Dusts a) b) Active compound mixture [Compound (A): 2% 5%Compound (I) to (XXXI) = 1:1] Highly disperse silicic acid 1% 5% Talc97% Kaolin 90%

Intimate mixing of the carriers with the active compounds givesready-to-use dusts.

Example F5: Wettable powders a) b) c) Active compound mixture [Compound(A): 25% 50% 75% Compound (I) to (XXXI) = 1:75] Sodium ligninsulfonate5% 5% Sodium lauryl sulfate 3%  5% Sodium diisobutylnaphthalenesulfonate6% 10% Octylphenol polyethylene glycol ether 2% — (7-8 mol of EO) Highlydisperse silicic acid 5% 10% 10% Kaolin 62% 27% —

The active compounds are mixed with the additives and ground thoroughlyin a suitable mill. Wettable powders which can be diluted with water togive suspensions of any desired concentration are obtained.

Example F6: Emulsion concentrate Active compound mixture [Compound (A):10% Compound (I) to (XXXI) = 1:350] Octylphenol polyethylene glycolether (4-5 mol of EO) 3% Calcium dodecylbenzenesulfonate 3% Castor oilpolyglycol ether (36 mol of EO) 4% Cyclohexanone 30% Xylene mixture 50%

Emulsions of any desired concentration can be prepared from thisconcentrate by dilution with water.

Example F7: Dusts a) b) Active compound mixture (2:3) 5%  8% Talc 95% —Kaolin 92%

Ready-to-use dusts are obtained by mixing the active compounds with thecarrier and grinding the mixture on a suitable mill.

Example F8: Extended granules Active compound mixture [Compound (A): 10%Compound (I) to (XXXI) = 1:4] Sodium ligninsulfonate 2%Carboxymethylcellulose 1% Kaolin 87%

The active compounds are mixed with the additives and the mixture isground and moistened with water. This mixture is extruded, granulatedand then dried in a stream of air.

Example F9: Coated granules Active compound mixture [Compound (A): 3%Compound (I) to (XXXI) = 1:300] Polyethylene glycol (molecular wt. 200)3% Kaolin 94%

The finely ground active compounds are applied uniformly to the kaolin,which is moistened with polyethylene glycol, in a mixer. Dust-freecoated granules are obtained in this way.

Example F10: Suspension concentrate Active compound mixture (2:350)  40%Ethylene glycol  10% Nonylphenol polyethylene glycol ether (15 mol ofEO)   6% Sodium ligninsulfonate  10% Carboxymethylcellulose   1% 37%aqueous formaldehyde solution 0.2% Silicone oil in the form of a 75%aqueous emulsion 0.8% Water  32%

The finely ground active compounds are mixed intimately with theadditives. A suspension concentrate from which suspensions of anydesired concentration can be prepared by dilution with water is thusobtained.

It is often more practical to formulate the active compound of theformula (A) and one of the mixing partners (I) to (XXXI) individuallyand then to bring them together in the applicator in the desired mixingratio as a “tank mix” in the water only shortly before application.

Biological Examples (%=percent by weight, unless stated otherwise)

A synergistic effect is always present if the action EA of thecombination of an active compound of the formula (A) with one of theactive compounds (I) to (XXXI) is greater than the sum of the action ofthe active compounds applied individually:

EA ₁ >X+Y (B)

However, the pesticidal action EA to be expected for a given combinationof two pesticides can also be calculated as follows (cf. COLBY, S. R.,“Calculating synergistic and antagonistic response of herbicidecombinations”, Weeds 15, Pages 20-22, 1967): $\begin{matrix}{{EA}_{2} = {X + \frac{Y\left( {100 - X} \right)}{100}}} & (C)\end{matrix}$

In this equation:

X=Percent mortality on treatment with the compound of the formula (A) ata rate of application of p kg per hectare compared with the untreatedcontrol (=0%).

Y=Percent mortality on treatment with a compound (I) to (XXXI) at a rateof application of q kg per hectare compared with the untreated control.

EA=Expected pesticidal action (percent mortality compared with theuntreated control) after treatment with the compound of the formula (A)and a compound (I) to (XXXI) at a rate of application of p+q kg ofactive compound per hectare.

If the action actually observed is greater than the expected value EA,synergism exists.

EXAMPLE B1

Action Against Bemisia tabaci

Dwarf bean plants are placed in gauze cages and populated with adults ofBemisia tabaci. After oviposition has taken place, all the adults areremoved. 10 days later, the plants with the nymphs on them are sprayedwith an aqueous suspension spray liquor comprising 50 ppm of the activecompound mixture. After a further 14 days, the percentage hatching ofthe eggs is evaluated in comparison with untreated control batches.

In this test, combinations of an active compound of the formula (A) withone of the active compounds (I) to (XXXI) have a synergistic effect. Inparticular, a suspension spray liquor which comprises 40 ppm of thecompound (A.1) and 10 ppm of the compound (II) has an activity of over80%.

EXAMPLE B2

Action Against Spodoptera littoralis Caterpillars

Young soya plants are sprayed with an aqueous emulsion spray liquorwhich comprises 360 ppm of the active compound mixture. After the spraycoating has dried on, the soya plants are populated with 10 caterpillarsof the third stage of Spodoptera littoralis and placed in a plasticcontainer. Evaluation takes place 3 days later. The percentage reductionin the population and the percentage reduction in feeding damage (%action) are determined from comparison of the number of deadcaterpillars and of the feeding damage on the treated plants with thoseon the untreated plants.

In this test, combinations of an active compound of the formula (A) withone of the active compounds (I) to (XXXI) have a synergistic effect. Inparticular, a suspension spray liquor which comprises 200 ppm of thecompound (A.2) and 160 ppm of the compound (II) and a suspension sprayliquor which comprises 180 ppm of the compound (A.3) and 180 ppm of thecompound (XV) have a good action.

EXAMPLE B3

Ovicidal Action on Lobesia botrana

Lobesia botrana eggs deposited on filter paper are immersed for a shorttime in an acetone-aqueous test solution comprising 400 ppm of theactive compound mixture to be tested. After the test solution has dried,the eggs are incubated in Petri dishes. After 6 days, the percentagehatching of the eggs is evaluated in comparison with untreated controlbatches (% reduction in hatching).

In this test, combinations of an active compound of the formula (A) withone of the active compounds (I) to (XXXI) have a synergistic effect. Inparticular, a suspension spray liquor which comprises 300 ppm of thecompound (A.5) and 100 ppm of the compound (III) and a suspension sprayliquor which comprise 200 ppm of the compound (A.5) and 200 ppm of thecompound (XVI) have an activity of over 80%.

EXAMPLE B4

Ovicidal Action on Heliothis virescens

Heliothis virescens eggs deposited on filter paper are immersed for ashort time in an acetone-aqueous test solution comprising 400 ppm of theactive compound mixture to be tested. After the test solution has dried,the eggs are incubated in Petri dishes. After 6 days, the percentagehatching of the eggs is evaluated in comparison with untreated controlbatches (% reduction in hatching).

In this test, combinations of an active compound of the formula (A) withone of the active compounds (I) to (XXXI) have a synergistic effect. Inparticular, a suspension spray liquor which comprises 240 ppm of thecompound (A.1) and 160 ppm of the compound (XII) and a suspension sprayliquor which comprise 300 ppm of the compound (A.5) and 100 ppm of thecompound (V) have an activity of over 80%.

EXAMPLE B5

Action Against Plutella xylostella Caterpillars

Young cabbage plants are sprayed with an aqueous emulsion spray liquorwhich comprises 440 ppm of the active compound. After the spray coatinghas dried on, the cabbage plants are populated with 10 caterpillars ofthe third stage of Plutella xylostella and placed in a plasticcontainer. Evaluation takes place 3 days later. The percentage reductionin the population and the percentage reduction in eating damage (%action) are determined from comparison of the number of deadcaterpillars and of the eating damage on the treated plants with thoseon the untreated plants.

In this test, combinations of an active compound of the formula (A) withone of the active compounds (I) to (XXXI) have a synergistic effect. Inparticular, a suspension spray liquor which comprises 400 ppm of thecompound (A.5) and 40 ppm of the compound (VII) and a suspension sprayliquor which comprises 220 ppm of the compound (A.7) and 220 ppm of thecompound (IV) have an activity of over 80%.

EXAMPLE B6

Action Against Myzus persicae

Capsicum plants (Capsicum annuum L.) 6 weeks old are sprayed with anaqueous emulsion spray liquor which comprises the individual compoundsand mixtures according to the following table. The plants were placed ina greenhouse until determination of the activity.

The activity against Myzus persicae was measured in bioassays. 2-4 hoursafter application, circles of leaf are stamped out, placed with theupper side down on agar in Petri dishes and infested with an M. persicaemixed population consisting of 40-50 non-synchronous individuals. Atotal of 9 circles of leaf per concentration are used. The Petri dishesare covered with a cotton wool filter, closed with a plastic lid andplaced in a climatically controlled chamber for plants. One day afterinfestation, the circles of leaf are cleaned of adults, skins andnymphs, so that only 25-40 nymphs laid overnight remain per circle ofleaf. Four days after infestation, the mortality is determined bycounting the dead and living nymphs. The tests are carried out 3 times.The results shown in the table are the average values of the tests.

TABLE Synergistic action of pesticide mixtures: M. persicae EA₁ EA₂ %calc. % calc. Conc., formula formula Compound/Mixture ppm Action % (B)(C) A.5  0.1  5.9 — — A.5  0.2 35.0 — — Profenofos  35 12.3 — —Cypermethrin high-cis 600  8.2 — — Pymetrozine  0.3 38.4 — —A.5/profenofos 0.1/35 31.4 18.2 17.5 A.5/cypermethrin high-cis 0.1/60022.8 14.1 13.6 A.5/cypermethrin high-cis 0.2/600 65.6 43.2 40.3A.5/pymetrozine 0.1/0.3 53.1 44.3 42.0

What is claimed is:
 1. A composition for controlling insects orrepresentatives of the order Acarina, which comprises an effectiveinsecticidal or acaricidal amount of a combination of one or morecompounds of the formula

in which A is a substituted or an unsubstituted thiazolyl group whereinthe substitution is by a halogen group and/or a C₁-C₃ alkyl group; R ishydrogen, C₁-C₆alkyl, phenyl-C₁-C₄alkyl, C₃-C₆cycloalkyl, C₂-C₆alkyenylor C₂-C₆alkynyl; and X is N—NO₂ in the free form or in salt from,optionally tautomers thereof, in the free form or salt form, and;pymetrozine; and at least one formulation auxiliary.
 2. A compositionaccording to claim 1 in which, in the compound of the formula (A), R isselected from the group consisting of hydrogen, C₁-C₄alkyl,C₃-C₈cycloalkyl, C₂-C₆alkenyl and C₂-C₆alkynyl.
 3. A compositionaccording to claim 1, which comprises:5(2-chlorothiazol-5-ylmethyl)-3-methyl-4-nitroimino-perhydro-1,3,5-oxadiazine.4. A method of controlling pests, which comprises applying a compositionas defined in claim 1 to the pests or their environment.
 5. A method ofprotecting plant propagation material which comprises treating the plantpropagation material or the site where the propagation material isbrought out, with the composition of claim
 1. 6. A process for thepreparation of a composition which comprises, intimately mixing theactive compounds according to claim 1 with at least one formulationauxiliary.